KF/Al2O3 as an efficient, green, and reusable catalytic system for the solvent-free synthesis of N-Alkyl derivatives of sulfonamides via michael reactions

Article abstract of DOI:10.1080/10426500802274625

KF/Al2O3 efficiently catalyzes the microwave-assisted Michael addition of sulfonamides to ,-unsaturated esters under solvent-free conditions to afford N-alkyl derivatives of sulfonamides as biologically interesting compounds in high yields and in short re

Full text of DOI:10.1080/10426500802274625

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Phosphorus, Sulfur, and Silicon
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KF/Al2O3 as an Efficient,
Green, and Reusable Catalytic
System for the Solvent-Free
Synthesis of N-Alkyl Derivatives
of Sulfonamides via Michael
Reactions
Abdolkarim Zare a , Alireza Hasaninejad b ,
Mohammad Hassan Beyzavi c , Ahmad Reza Moosavi-
Zare c , Ali Khalafi-Nezhad c , Mehrnoosh Roshankar a
, Fatemeh Fiouzi a & Sedigheh Azad a
a Department of Chemistry , Payame Noor University
(PNU) , Bushehr, Iran
b Department of Chemistry, Faculty of Sciences ,
Persian Gulf University , Bushehr, Iran
c Department of Chemistry, College of Sciences ,
Shiraz University , Shiraz, Iran
Published online: 22 Jun 2009.
To cite this article: Abdolkarim Zare , Alireza Hasaninejad , Mohammad Hassan
Beyzavi , Ahmad Reza Moosavi-Zare , Ali Khalafi-Nezhad , Mehrnoosh Roshankar ,
Fatemeh Fiouzi & Sedigheh Azad (2009) KF/Al2O3 as an Efficient, Green, and Reusable
Catalytic System for the Solvent-Free Synthesis of N-Alkyl Derivatives of Sulfonamides
via Michael Reactions, Phosphorus, Sulfur, and Silicon and the Related Elements,
184:7, 1702-1712, DOI: 10.1080/10426500802274625
To link to this article: http://dx.doi.org/10.1080/10426500802274625

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Phosphorus, Sulfur, and Silicon, 184:1702–1712, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802274625
KF/Al2O3 as an Efficient, Green, and Reusable Catalytic
System for the Solvent-Free Synthesis of N-Alkyl
Derivatives of Sulfonamides via Michael Reactions
Abdolkarim Zare,1 Alireza Hasaninejad,2
Mohammad Hassan Beyzavi,3 Ahmad Reza Moosavi-Zare,3
Ali Khalafi-Nezhad,3 Mehrnoosh Roshankar,1
Fatemeh Fiouzi,1 and Sedigheh Azad1
1Department of Chemistry, Payame Noor University (PNU),
Bushehr, Iran
2Department of Chemistry, Faculty of Sciences, Persian Gulf University,
Bushehr, Iran
3Department of Chemistry, College of Sciences, Shiraz University,
Shiraz, Iran
KF/Al O efficiently catalyzes the microwave-assisted Michael addition of sulfon-
2
3
amides to α,β-unsaturated esters under solvent-free conditions to afford N-alkyl
derivatives of sulfonamides as biologically interesting compounds in high yields
and in short reaction times. In this reaction, N,N-dialkylsulfonamides are also
produced, but in very low yields.
Keywords N-alkylsulfonamide; KF/Al2O3; Michael addition; microwave; solvent-free;
sulfonamide
INTRODUCTION
In recent years, evolution of chemical reactions involving less haz-
ardous, environmentally acceptable, and recyclable catalytic systems
has gained considerable attention both in industrial and academia
research.1,2 KF/Al2O3 is one of the green catalytic systems that
has been used in various organic transformations such as syn-
thesis of pyrano[3,2-c]pyran derivatives,2a alkylation and arylation
Received 28 April 2008; accepted 15 June 2008.
The authors thank Payame Noor University (PNU) and Persian Gulf Research Coun-
cils for the financial support of this work.
Address correspondence to Abdolkarim Zare, Department of Chemistry, Payame Noor
University (PNU), Bushehr 1698, Iran. E-mail: abdolkarimzare@yahoo.com or Alireza
Hasaninejad, Department of Chemistry, Faculty of Sciences, Persian Gulf University,
Bushehr 75169, Iran. E-mail: ahassaninejad@yahoo.com
1702

Synthesis of N-Alkylsulfonamides
1703
reactions,2b–2d hydrothilation of alkynes,2e cycloaddition of azomethine
ylides,2f deformylation of N-arylformamides,2g conversion of aldehy-
des to nitriles,2h acetylation of amines, alcohols and phenols,2i syn-
thesis of oxazolidinones,2j desilylation reactions,2k etc.2l Nevertheless,
most of the existing processes in organic synthesis involve toxic and
volatile organic solvents as reaction media, and these are environmen-
tally unacceptable from a green chemistry viewpoint. One useful tech-
nique to solve this problem is the use of solvent-free conditions that
makes synthesis simpler, saves energy, and prevents solvent waste,
hazards, and toxicity.3 Together with the removal of the solvent, non-
conventional activation methods, mainly microwave irradiation, have
been applied as powerful techniques to reduce reaction times and to
increase yields.3 Consequently, it is important to note that the combi-
nation of safe catalysis with the use of solventless technology under mi-
crowave irradiation represents a suitable way toward the so-called ideal
synthesis.
N-Alkylsulfonamides are significant because of their biological activ-
ities including analgesic, anti-depressant, psychostimulant, anti-ulcer,
anti-emetic, and anti-inflammatory properties.4 Aza-Michael addition
of sulfonamides to electrophilic alkenes can be used as a synthetic route
toward N-alkylated sulfonamides. However, this reaction has not been
extensively studied to date.5 Reitz et al. have used Al2O3 to achieve
Michael addition of sulfonamides to α,β-unsaturated ketones5a; how-
ever, this catalyst was not efficient when less reactive α,β -unsaturated
esters were used.5b Furthermore, the reaction times are long and
the yields are moderate. Gimbert et al. have carried out the Michael
addition of sulfonamides to electrophilic alkenes in the presence of
PBu3.5c In this work, only N, N-dialkyl derivatives of sulfonamides
were prepared in relatively long reaction times. Moreover, more re-
cently, we have applied MgO/[bmim]Br,5b ZnO/[bmim]Br,5d and K2CO53e
for Michael addition of sulfonamides to α,β -unsaturated esters. These
reports are associated with one or more of the following drawbacks: (i)
the use of relatively expensive ionic liquids, (ii) moderate selectivity
in the synthesis of N-alkyl and N, N-dialkylsulfonamides, and (iii) the
necessity of a stoichiometric amount of catalyst.
In this article, we report a simple method for the synthesis of N-
alkylated sulfonamides via Michael addition of sulfonamides to α,β-
unsaturated esters in the presence KF/Al2O3 (as a highly efficient,
green, heterogeneous, and recyclable catalytic system) and tetrabuty-
lammonium bromide (TBAB) under solvent-free and microwave irra-
diation conditions (Scheme 1). It is worth noting that this method has
none at all of the above-mentioned disadvantages.

1704
A. Zare et al.
O
O
O
OBu
OBu
OBu
O
S
O
S
O
KF/Al2O3, TBAB
MW, 300 W, 110 °C
Ph
NH2
+
+
Ph
N
Ph
S
NH
CO2Bu
O
O
O
1a
2b
2c
2d
SCHEME 1
RESULTS AND DISCUSSION
To optimize the reaction conditions, we first studied the effect of dif-
ferent molar ratios of KF/Al2O3 on the Michael addition of benzene-
sulfonamide (2 mmol) to n-butyl acrylate (2.2 mmol) in the presence
of TBAB (0.5 mmol) under solvent-free and microwave conditions (300
W, max. 110◦C) (Scheme 1). The results are summarized in Table I. As
can be seen from the data in Table I, the best molar ratio of KF/Al2O3
was 25 mol%. The model reaction was also examined in the presence
of KF/TBAB as well as Al2O3/TBAB separately (Table II). As the data
in Table II indicate, the selectivity of the reaction decreased remark-
ably when KF/TBAB was used. Moreover, Al2O3/TBAB afforded low
yields of both N-alkyl and N, N-dialkylsulfonamides. In another study,
the influence of TBAB on the reaction was investigated. The selectiv-
ity was decreased when TBAB was removed from the reaction media
(Table II). Thus, TBAB has an essential effect on the selectivity of the
reaction. The reaction of benzenesulfonamide with n-butyl acrylate was
also examined in the presence of TBAB without KF/Al2O3; however,
this reaction was not successful and compound 2c was produced in
trace yield (Table II).
TABLE I The Effect of Different Amounts of KF/Al2O3 on
Reaction of Benzenesulfonamide with n-Butyl Acrylate in the
Presence of TBAB Under Microwave Irradiation (300 W, Max.
110◦C)
Yield (%)a
N-Alkylated
product 2c
N,N-Dialkylated
pruduct 2d
KF/Al2O3 (mol%)
Time (min)
15
25
40
60
15
9
8
79
92
71
62
5
6
18
23
6
aIsolated yield.

Synthesis of N-Alkylsulfonamides
1705
TABLE II Michael Addition of Benzenesulfonamide to
n-Butyl Acrylate Using KF/TBAB, Al2O3/TBAB, KF/Al2O3 and
TBAB Separately Under Microwave Irradiation (300 W, Max.
110◦C)
Yield (%)a
N-Alkylated
product 2c
N,N-Dialkylated
pruduct 2d
Catalytic system
Time (min)
KF/TBAB
Al2O3/TBAB
KF/Al2Ob3
TBABc
10
15
17
20
39
33
43
34
5
31
—
Trace
aIsolated yield.
bThis reaction was carried out in the absence of TBAB.
cThis reaction was performed in the presence of TBAB without KF/Al2O3.
In order to select a suitable microwave power for the reaction, the
Michael addition of benzenesulfonamide to n-butyl acrylate was exam-
ined in the presence of KF/Al2O3 and TBAB at different microwave
powers (100–600 W) with controlled temperature (max. 110◦C). The
best results were observed at 300 W.
The efficiency and capacity of the solvent-free procedure, in compar-
ison to solution condition, was also studied. For this purpose, a mix-
ture of benzenesulfonamide (2 mmol), KF/Al2O3 (25 mol%), TBAB (0.5
mmol), and n-butyl acrylate (2.2 mmol) was irradiated in a microwave
oven (300 W, max. 110◦C) in different solvents (2 mL) (Table III). As it
TABLE III Comparative the Reaction of
Benzenesulfonamide with n-Butyl Acrylate in the
Presence of KF/Al2O3 and TBAB Under Solution
Conditions Versus the Solvent-Free Method
Yield (%)a
Time
(min)
N-Alkylated
product 2c
N,N-Dialkylated
Solvent
product 2d
Solvent-free
DMF
DMSO
9
9
9
92
81
40
27
6
13
29
10
o-Xylene
15
aIsolated yield.

1706
A. Zare et al.
can be seen from the data in Table III, the solvent-free method afforded
higher yield and selectivity.
To demonstrate the effectiveness of microwave irradiation with re-
spect to conventional heating, the reaction between benzenesulfon-
amide (2 mmol) and n-butyl acrylate (2.2 mmol) in the presence of
KF/Al2O3 (25 mol%) and TBAB (0.5 mmol) was examined in an oil bath
(110◦C). However, the reaction was not complete under these conditions
after 8 h, and the Michael adducts 2c and 2d were obtained in 65% and
13%, respectively. The results were not improved by increasing the re-
action time and the temperature. Therefore, microwave irradiation is
essential to promote this reaction.
After optimization of the reaction conditions, sulfonamides were re-
acted with structurally diverse α,β -unsaturated esters. The results are
displayed in Table IV. As the data in Table IV demonstrate, all reactions
proceeded efficiently, and the desired Michael adducts were obtained
in high yields and in short reaction times. In addition, the selectivity
was excellent in all reactions. It has been observed that the type of
alkoxy group (-OR) in the α,β -unsaturated esters does not significantly
affect the yields, the selectivities, or the reaction times (Table IV, en-
tries 1–8). When benzenesulfonamide was added to sterically hindered
α,β -unsaturated esters (ethyl methacrylate and ethyl crotonate), the
yields decreased and the reaction times increased (Table IV, entries 9–
12). Nevertheless, in these reactions the selectivity increased. Interest-
ingly, Michael addition of benzenesulfonamide as well as naphthalene-
2-sulfonamide to ethyl crotonate afforded only monosubstituted prod-
uct (Table IV, entries 11 and 12). Furthermore, the type of sulfonamide
had no significant effect on the reaction results.
The interesting behavior of the KF/Al2O3 system lies in the fact that
it can be reused after simple washing with warm CHCl3, thus rendering
the process more economical. The yields of compounds 2c and 2d (model
compounds) in the second, third, and fourth uses of the KF/Al2O3 were
almost as high as in the first use.
In summary, we have developed an efficient method for the synthe-
sis of N-alkylsulfonamides via Michael reactions. This new strategy
has several advantages, such as high yields, high selectivity, short re-
action times, low cost, simple experimental as well as straightforward
isolation, and finally, agreement with the green chemistry protocol.
EXPERIMENTAL
All chemicals were purchased from Merck or Fluka Chemical Compa-
nies. All reactions were carried out using a laboratory microwave oven

Synthesis of N-Alkylsulfonamides
1707
TABLE IV Synthesis of N-Alkylsulfonamides via Michael Addition
Reaction Using KF/Al2O3 and TBAB Under Microwave Irradiation
(300 W, 110◦C)
R
R'
R
N
R'
O
S
O
S
O
R
R'
KF/Al2O3 (25 mol%), TBAB
MW, 300 W, 110 °C
CO2R"
+
Ar
NH2
Ar
NH
CO2R"
+
Ar
S
O
R'
CO2R"
R
O
O
CO2R"
1d-10d
1a-3a
1b-8b
1c-12c
Time
(min)
Yield
(%)b
Entry
1c
Ar
R
Rꢀ
H
Rꢀꢀ
CH3CH2
Producta
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
H
H
H
H
H
H
H
H
1c
1d
2c
2d
3c
3d
4c
4d
5c
5d
6c
6d
7c
7d
8c
8d
9
89
6
92
6
91
6
90
6
89
5
90
5
92
5
91
2
3
4
5
6
7
8
H
H
H
H
H
H
H
CH3(CH2)2CH2
CH3(CH2)4CH2
C6H5CH2
9
10
11
12
13
12
10
C6H5CH2CH2
C6H5CH=CHCH2
CH3(CH2)2CH2
CH3(CH2)4CH2
p-CH3C6H4
6
9
C6H5
p-CH3C6H4
C6H5
H
H
CH3
CH3
CH3CH2
CH3CH2
9c
9d
10c
10d
11c
12c
18
18
81
4
85
4
77
74
10
11d
12d
CH3
CH3
H
H
CH3CH2
CH3CH2
24
24
aAll known compounds were identified by comparison of their spectral data with
those in the authentic samples.
bIsolated yield.
cIn this reaction, the α,β -unsaturated esters/sulfonamide (mol/mol) ratio was 1.3:1.
dThis reaction was performed at 120◦C (300 W).
(MW 3000, Landgraf Company, Germany). The 1H NMR (250 MHz) and
13C NMR (62.5 MHz) were run on a Bruker Avance DPX-250, FT-NMR
spectrometer. Mass spectra were recorded on a Shimadzu GC MS-QP
1000 EX apparatus. Microanalyses were performed on a Perkin-Elmer
¨
240-B microanalyzer. Melting points were recorded on a Buchi B-545
apparatus in open capillary tubes.

1708
A. Zare et al.
Procedure for the Preparation of the KF/Al2O3
Catalytic System
A mixture of KF (0.291 g, 5 mmol) and Al2O3 (0.510, 5 mmol) was
ground vigorously to give the KF/Al2O3 catalytic system as a white
powder (0.801 g).
General Procedure for the Synthesis of N-Alkyl Derivatives of
Sulfonamides via Michael Reaction
A well-ground mixture of sulfonamide (2 mmol), KF/Al2O3 (0.080 g,
0.5 mmol, 25 mol%), and TBAB (0.161 g, 0.5 mmol) was placed in
a microwave vessel, and then α,β -unsaturated ester (2.2 mmol) was
added and mixed carefully with a small rod. The resulting mixture was
irradiated in a microwave oven at 300 W (max. 110◦C) for the times
reported in Table IV. Subsequently, the reaction mixture was cooled to
room temperature and suspended in chloroform (60 mL), filtered, the
filtrate washed with water (2 × 50 mL), and then dried over anhydrous
MgSO4. The solvent was evaporated, and the crude product was purified
by column chromatography on silica gel eluting with EtOAc:n-hexane
(1:3). After isolation of the products, the remaining KF/Al2O3 was dried
and used for the next run under identical reaction conditions.
Ethyl 3-(Phenylsulfonamido)propanoate (1c)
1
Colorless oil (Lit.5b oil); H NMR (CDCl3): δ 1.16 (t, 3H, J = 7.0 Hz,
CH3), 2.48 (t, 2H, J = 5.0 Hz, CH2CO), 3.15 (t, 2H, J = 5.0 Hz, CH2N),
4.02 (q, 2H, J = 7.0 Hz, CH2O), 5.56 (s, 1H, NH), 7.42-7.52 (m, 3H,
3,4,5-HPh), 7.80 (m, 2H, 2,6-HPh).
Diethyl 3,3ꢀ-(Phenylsulfonylazanediyl)dipropanoate (1d)
1
Colorless oil (Lit.5b oil); H NMR (CDCl3): δ 1.22 (t, 6H, J = 7.1 Hz,
2CH3), 2.59 (t, 4H, J = 5.0 Hz, 2CH2CO), 3.45 (t, 4H, J = 5.0 Hz,
CH2NCH2), 4.08 (q, 4H, J = 7.1 Hz, 2CH2O), 7.46-7.57 (m, 3H, 3,4,5-
HPh), 7.87 (m, 2H, 2,6-HPh).
Butyl 3-(Phenylsulfonamido)propanoate (2c)
1
Colorless oil (Lit.5b oil); H NMR (CDCl3): δ 0.90 (t, 3H, J = 6.5 Hz,
CH3), 1.34 (m, 2H, CH3CH2), 1.56 (m, 2H, CH3CH2CH2), 2.51 (t, 2H,
J = 5.0 Hz, CH2CO), 3.19 (t, 2H, J = 5.0 Hz, CH2N), 4.03 (t, 2H, J =
7.0 Hz, CH2O), 5.68 (s, 1H, NH), 7.48–7.57 (m, 3H, 3,4,5-HPh), 7.79 (m,
2H, 2,6-HPh).
Dibutyl 3,3ꢀ-(Phenylsulfonylazanediyl)dipropanoate (2d)
1
Colorless oil (Lit.5b oil); H NMR (CDCl3): δ 0.92 (t, 6H, J = 6.5 Hz,
2CH3), 1.33 (m, 4H, 2CH3CH2), 1.56 (m, 4H, 2CH3CH2CH2), 2.63 (t,

Synthesis of N-Alkylsulfonamides
1709
4H, J = 5.1 Hz, 2CH2CO), 3.45 (t, 4H, J = 5.1 Hz, CH2NCH2), 4.06
(t, 4H, J = 6.9 Hz, 2CH2O), 7.51–7.60 (m, 3H, 3,4,5-HPh), 7.82 (m, 2H,
2,6-HPh).
Hexyl 3-(Phenylsulfonamido)propanoate (3c)
1
Colorless oil (Lit.5d oil); H NMR (CDCl3): δ 0.90 (t, 3H, J = 6.7 Hz,
CH3), 1.28–1.34 (m, 6H, CH3CH2, CH3CH2CH2 and CH3(CH2)2CH2),
1.57 (m, 2H, CH3(CH2)3CH2), 2.56 (t, 2H, J = 5.1 Hz, CH2CO), 3.16 (t,
2H, J = 5.1 Hz, CH2N), 4.09 (t, 2H, J = 6.9 Hz, CH2O), 5.63 (s, 1H,
NH), 7.41–7.48 (m, 3H, 3,4,5-HPh), 7.78 (m, 2H, 2,6-HPh).
Dihexyl 3,3ꢀ-(Phenylsulfonylazanediyl)dipropanoate (3d)
Colorless oil (Lit.5d oil); 1H NMR (CDCl3): δ 0.89 (t, 6H, J =
6.6 Hz, 2CH3), 1.26–1.32 (m, 12H, 2CH3CH2, 2CH3CH2CH2 and
2CH3(CH2)2CH2), 1.58 (m, 4H, 2CH3(CH2)3CH2), 2.61 (t, 4H, J = 5.0
Hz, 2O=CCH2), 3.41 (t, 4H, J = 5.0 Hz, CH2NCH2), 4.05 (t, 4H, J = 6.9
Hz, 2CH2O), 7.43–7.50 (m, 3H, 3,4,5-HPh), 7.74 (m, 2H, 2,6-HPh).
Benzyl 3-(Phenylsulfonamido)propanoate (4c)
Pale yellow oil (Lit.5e oil); 1H NMR (CDCl3): δ 2.65 (t, 2H, J = 5.1 Hz,
CH2CO), 3.17 (t, 2H, J = 5.1 Hz, CH2N), 5.00 (s, 2H, CH2O), 5.71 (s,
1H, NH), 7.26–7.31 (m, 5H, HPhC), 7.45–7.51 (m, 3H, 3,4,5-HPhS), 7.82
(m, 2H, 2,6-HPhS).
Dibenzyl 3,3ꢀ-(Phenylsulfonylazanediyl)dipropanoate (4d)
1
Pale yellow oil (Lit.5e oil); H NMR (CDCl3): δ 2.58 (t, 4H, J = 5.0
Hz, 2CH2CO), 3.36 (t, 4H, J = 5.0 Hz, CH2NCH2), 5.00 (s, 4H, 2CH2O),
7.22–7.25 (m, 10H, HPhC), 7.39–7.48 (m, 3H, 3,4,5-HPhS), 7.72 (m, 2H,
2,6-HPhS).
Phenethyl 3-(Phenylsulfonamido)propanoate (5c)
1
Pale yellow oil (Lit.5b oil); H NMR (CDCl3): δ 2.48 (t, 2H, J = 5.2,
CH2CO), 2.88 (t, 2H, J = 6.8 Hz, CH2Ph), 3.14 (t, 2H, J = 5.2 Hz,
CH2N), 4.24 (t, 2H, J = 6.8 Hz, CH2O), 5.43 (s, 1H, NH), 7.15–7.28 (m,
5H, HPhC), 7.47–7.52 (m, 3H, 3,4,5-HPhS), 7.81–7.86 (m, 2H, 2,6-HPhS).
Diphenethyl 3,3ꢀ-(Phenylsulfonylazanediyl)dipropanoate (5d)
Pale yellow oil (Lit.5b oil); 1H NMR (CDCl3): δ 2.51 (t, 4H, J = 5.2 Hz,
2CH2CO), 2.82 (t, 4H, J = 6.9 Hz, 2CH2Ph), 3.30 (t, 4H, J = 5.2 Hz,
CH2NCH2), 4.19 (t, 4H, J = 6.9 Hz, 2CH2O), 7.10-7.19 (m, 10H, HPhC),
7.42–7.45 (m, 3H, 3,4,5-HPhS), 7.7–7.82 (m, 2H, 2,6-HPhS).

1710
A. Zare et al.
Cinnamyl 3-(Phenylsulfonamido)propanoate (6c)
Pale yellow oil (Lit.5e oil); 1H NMR (CDCl3): δ 2.55 (t, 2H, J = 5.2 Hz,
CH2CO), 3.19 (t, 2H, J = 5.2 Hz, CH2N), 4.69 (m, 2H, CH2O), 5.50 (s,
1H, NH), 6.23 (m, 1H, =CHCH2), 6.63 (d, 1H, J = 15.7 Hz, =CHPh),
7.29–7.35 (m, 5H, HPhC), 7.45–7.50 (m, 3H, 3,4,5-HPhS), 7.95 (m, 2H,
2,6-HPhS).
Dicinnamyl 3,3ꢀ-(Phenylsulfonylazanediyl)dipropanoate (6d)
Pale yellow oil (Lit.5e oil); 1H NMR (CDCl3): δ 2.51 (t, 4H, J = 5.1 Hz,
2CH2CO), 3.41 (t, 4H, J = 5.1 Hz, CH2NCH2), 4.73 (m, 4H, 2CH2O),
6.15 (m, 2H, 2=CHCH2), 6.54 (d, 2H, J = 15.7 Hz, 2=CHPh), 7.28–7.36
(m, 10H, HPhC), 7.41–7.47 (m, 3H, 3,4,5-HPhS), 7.94 (m, 2H, 2,6-HPhS).
Butyl 3-(4-Methylphenylsulfonamido)propanoate (7c)
Pale yellow oil (Lit.5d oil); 1H NMR (CDCl3): δ 0.89 (t, 3H, J = 6.8 Hz,
CH3CH2), 1.33 (m, 2H, CH3CH2), 1.56 (m, 2H, CH3CH2CH2), 2.40 (s,
3H, CH3Ar), 2.51 (t, 2H, J = 5.3 Hz, CH2CO), 3.16 (t, 2H, J = 5.3 Hz,
CH2N), 4.04 (t, 2H, J = 7.0 Hz, CH2O), 5.76 (s, 1H, NH), 7.33 (d, 2H,
J = 7.9 Hz, 3,5-HAr), 7.72 (d, 2H, J = 7.9 Hz, 2,6-HAr).
Dibutyl 3,3ꢀ-(Tosylazanediyl)dipropanoate (7d)
1
Pale yellow oil (Lit.5d oil); H NMR (CDCl3): δ 0.92 (t, 6H, J = 6.9
Hz, 2CH3CH2), 1.32 (m, 4H, 2CH3CH2), 1.57 (m, 4H, 2CH3CH2CH2),
2.42 (s, 3H, CH3Ar), 2.63 (t, 4H, J = 5.2 Hz, 2CH2CO), 3.43 (t, 4H, J =
5.2 Hz, CH2NCH2), 4.02 (t, 4H, J = 7.0 Hz, 2CH2O), 7.31 (d, 2H, J =
7.9 Hz, 3,5-HAr), 7.72 (d, 2H, J = 7.9 Hz, 2,6-HAr).
Hexyl 3-(Naphthalene-2-sulfonamido)propanoate (8c)
1
Pale yellow oil; H NMR (CDCl3): δ 0.89 (t, 3H, J = 6.7 Hz, CH3),
1.31–1.38 (m, 6H, CH3CH2, CH3CH2CH2 and CH3(CH2)2CH2), 1.60 (m,
2H, CH3(CH2)3CH2), 2.58 (t, 2H, J = 5.0 Hz, CH2CO), 3.18 (t, 2H, J =
5.0 Hz, CH2N), 4.11 (t, 2H, J = 6.8 Hz, OCH2), 5.56 (s, 1H, NH), 7.54–
7.65 (m, 4H, HAr), 7.85–7.95 (m, 3H, HAr); 13C NMR (CDCl3): δ 13.9,
22.4, 25.8, 28.5, 31.2, 34.3, 38.5, 65.8, 123.1, 126.5, 126.9, 127.3, 127.5,
127.7, 128.3, 129.0, 129.2, 131.9, 172.3; MS (m/z): 363 (M+); Anal. calcd.
for C19H25NO4S: C, 62.78; H, 6.93; N, 3.85. Found: C, 62.97; H, 7.16; N,
3.72.
Dihexyl 3,3ꢀ-(Naphthalene-2-sulfonylazanediyl)dipropanoate
(8d)
1
Pale yellow oil, H NMR (CDCl3): δ 0.91 (t, 6H, J = 6.7 Hz, 2CH3),
1.28–1.33 (m, 12H, 2CH3CH2, 2CH3CH2CH2 and 2CH3(CH2)2CH2),

Synthesis of N-Alkylsulfonamides
1711
1.56 (m, 4H, 2CH3(CH2)3CH2), 2.57 (t, 4H, J = 5.1 Hz, 2CCH2O), 3.44
(t, 4H, J = 5.1 Hz, 2CH2N), 4.10 (t, 4H, J = 6.7 Hz, 2OCH2), 7.50–7.59
(m, 4H, HAr), 7.82–7.93 (m, 3H, HAr); 13C NMR (CDCl3): δ 14.1, 22.6,
26.4, 28.6, 30.9, 33.5, 43.7, 65.1, 122.8, 126.6, 127.1, 127.4, 127.7, 127.9,
128.4, 129.3, 129.4, 131.5, 171.8; MS (m/z): 418 (M+ -C6H13O); Anal.
calcd. for C28H41NO6S: C, 64.71; H, 7.95; N, 2.70. Found: C, 64.90; H,
7.78; N, 2.94.
Ethyl 2-Methyl-3-(phenylsulfonamido)propanoate (9c)
Pale yellow oil (Lit.5b oil); 1H NMR (CDCl3): δ 1.17–1.26 (m, 6H,
2CH3), 2.73 (m, 1H, CHCO), 3.14–3.20 (m, 2H, CH2N), 4.12 (q, 2H, J =
7.0 Hz, CH2O), 5.65 (s, 1H, NH), 7.55–7.64 (m, 3H, 3,4,5-HPh), 7.93 (m,
2H, 2,6-HPh).
Diethyl 3,3ꢀ-(Phenylsulfonylazanediyl)bis(2-methylpropanoate)
(9d)
1
Pale yellow oil (Lit.5b oil); H NMR (CDCl3): δ 1.09–1.19 (m, 12H,
4CH3), 2.78 (m, 2H, 2CHCO), 3.22–3.27 (m, 4H, CH2NCH2), 4.03 (q,
4H, J = 7.0 Hz, 2CH2O), 7.44–7.53 (m, 3H, 3,4,5-HPh), 7.75 (m, 2H, 2,6-
HPh).
Ethyl 2-Methyl-3-(4-methylphenylsulfonamido)propanoate
(10c)
1
Pale yellow oil; H NMR (CDCl3): δ 1.24–1.30 (m, 6H, 2CH3), 2.48
(s, 3H, CH3Ar), 2.78 (m, 1H, CHCO), 3.16–3.19 (m, 2H, CH2N), 4.08 (q,
2H, J = 7.1 Hz, CH2O), 5.72 (s, 1H, NH), 7.29 (d, 2H, J = 7.9 Hz, 3,5-
HAr), 7.74 (d, 2H, J = 7.9 Hz, 2,6-HAr); 13C NMR (CDCl3): δ 14.2, 14.6,
19.6, 39.2, 44.7, 64.2, 127.8, 129.5, 136.4, 142.7, 171.5; MS (m/z): 285
(M+); Anal. calcd. for C13H19NO4S: C, 54.72; H, 6.71; N, 4.91. Found: C,
54.51; H, 6.96; N, 4.76.
Diethyl 3,3ꢀ-(Tosylazanediyl)bis(2-methylpropanoate) (10d)
1
Pale yellow oil; H NMR (CDCl3): δ 1.15–1.23 (m, 12H, 4CH3), 2.43
(s, 3H, CH3Ar), 2.74 (m, 2H, 2CHCO), 3.18–3.24 (m, 4H, CH2NCH2),
4.07 (q, 4H, J = 7.0 Hz, 2CH2O), 7.30 (d, 2H, J = 7.9 Hz, 3,5-HAr), 7.75
(d, 2H, J = 7.9 Hz, 2,6-HAr); 13C NMR (CDCl3): δ 14.0, 14.9, 19.4, 40.1,
51.2, 63.9, 128.0, 130.1, 136.1, 143.1, 172.3; MS (m/z): 399 (M+); Anal.
calcd. for C19H29NO6S: C, 57.12; H, 7.32; N, 3.51. Found: C, 56.95; H,
7.08; N, 3.32.

1712
A. Zare et al.
Ethyl 3-(Phenylsulfonamido)butanoate (11c)
Pale yellow solid; mp 61–63◦C (Lit.5e mp 60–62◦C); 1H NMR (CDCl3):
δ 1.14–1.23 (m, 6H, 2CH3), 2.38–2.43 (m, 2H, CH2CO), 3.68 (m, 1H,
CHN), 4.04 (q, 2H, J = 7.1 Hz, CH2O), 5.39 (s, 1H, NH), 7.49–7.59 (m,
3H, 3,4,5-HPh), 7.89 (m, 2H, 2,6-HPh).
Ethyl 3-(Naphthalene-2-sulfonamido)butanoate (12c)
Buff oil (Lit.5b buff oil); 1H NMR (CDCl3): δ 1.07–1.12 (m, 6H, 2CH3),
2.31–2.35 (m, 2H, CH2CO), 3.67 (m, 1H, CHN), 3.99 (q, 2H, J = 7.0
Hz, CH2O), 5.38 (s, 1H, NH), 7.52–7.57 (m, 4H, HAr), 7.79–7.90 (m, 3H,
HAr).
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